Synthetic Applications of the Carbonyl Generating Grob Fragmentation

Prantz, Kathrin; Mulzer, Johann

Chemical Reviews (Washington, DC, United States) (2010), 110(6), 3741-3766.

1. Introduction
- 1.1. History
- 1.2. General Mechanistic Considerations
2. Carbonyl Generating Grob Fragmentation via Ring Cleavage
- 2.1. Monosulfated 1,3-Diols
- 2.2. β-Hydroxy Ketones
- 2.3. Bromide/Iodide as Leaving Group
- 2.4. Ammonium as Leaving Group
- 2.5. Acetals
- 2.6. 3,4-Epoxy Alcohols as Fragmentation Substrates
- 2.7. Miscellaneous
3. Carbonyl Generating Grob Fragmentation via Ring Expansions
- 3.1. Monosulfated 1,3-Diols
- 3.2. β-Hydroxy Ketones
- 3.3. Enolate-Induced Grob Fragmentation
- 3.4. Fragmentation of 3,4-Epoxy Alcohols
- 3.5. Ammonium Ions as Leaving Group
- 3.6. Miscellaneous
- 3.7. Miscellaneous without Electrofugal Carbonyl Groups
4. Decarboxylative Fragmentations
5. Tandem Reactions
- 5.1. Tandem Aldol−Grob Fragmentation Sequence(124, 125)
- 5.2. Sequential Semipinacol Rearrangement/Grob Fragmentation of Allylic Alcohols(126)
- 5.3. Intramolecular Barbier Cyclization/Grob Fragmentation(127)
- 5.4. Grob Fragmentation/Michael Addition(128)
- 5.5. Intramolecular Aldol Reaction/Acetalization/Grob Fragmentation(129)
- 5.6. Intermolecular Aldol Reaction/Acetalization/Grob Fragmentation(130)
- 5.7. Haller/Bauer-Scission/Grob Fragmentation(133)
- 5.8. Trapping of Primary Ozonides(134)
- 5.9. Construction of the Core of Zaragozic Acids
- 5.10. Grob Fragmentation Followed by a Transannular Ketene [2 + 2] Cycloaddition Reaction(136)
- 5.11. Grob Fragmentation and Stereocontrolled SmI2-Mediated Cyclization(137, 138)
- 5.12. Free Radical Fragmentation/Elimination Sequence(139)
6. Fragmentation as Unexpected Side Reaction
- 6.1. Kempane Diterpenes(141)
- 6.2. Diels−Alder Adducts of Acetoxy-1,3-dienes and p-Benzoquinone(142)
7. Summary and Conclusions

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Johann Mulzer
Institute for Organic Chemistry
University of Vienna

Währingerstraße 38
A-1090 Vienna